KR102400677B1 - Resin compositions - Google Patents

Abstract

[Problem] A resin composition in which warpage is suppressed and excellent in strength and adhesion; Provision of a resin sheet, a circuit board, and a semiconductor chip package using the same.
[Solutions] (a) an elastomer having a polycarbonate structure in a molecule, (b) an epoxy resin, (c) an inorganic filler, (d) a phenoxy resin, and (e) a resin composition containing a carbodiimide compound, etc. will be.

Description

Resin composition {RESIN COMPOSITIONS}

The present invention relates to a resin composition. Moreover, it is related with the resin sheet, circuit board, and semiconductor chip package which used the resin composition.

In recent years, the demand for small high-performance electronic devices such as smartphones and tablet PCs is increasing, and accordingly, the insulating material (insulating layer) for semiconductor packages used in these small-sized electronic devices is also required to be highly functional.

For example, an insulating layer for die sealing used in a fan-out type wafer-level chip size package (Wafer Level Package) suppresses warpage, sufficient strength when peeling a resin wafer from a temporary fixing tape, and insulation for rewiring Sufficient adhesiveness to a layer (eg, silicon nitride, polyimide, etc.) is calculated|required. Moreover, suppression of curvature, sufficient intensity|strength at the time of peeling a core board|substrate, and sufficient adhesiveness with respect to copper are calculated|required of the insulating layer used for the wiring board provided with a buried wiring layer.

Patent Document 1 discloses a thermosetting resin composition containing a specific linearly modified polyimide resin and a thermosetting resin as a low elastic modulus thermosetting resin composition. However, the current situation is that the design of the resin composition is limited from the viewpoint of compatibility with other resins for such a low elastic modulus insulating material, and it has not reached the point of satisfying the required properties.

Patent Document 1: Japanese Patent Laid-Open No. 2006-37083

This invention was made in order to solve the said subject, and it is providing the resin composition which curvature is suppressed and is excellent in intensity|strength and adhesiveness, the resin sheet using this resin composition, a circuit board, and a semiconductor chip package.

The present inventors have found that (a) an elastomer having a polycarbonate structure in a molecule, (b) an epoxy resin, (c) an inorganic filler, (d) a phenoxy resin, and (e) a resin composition containing a carbodiimide compound, It was discovered that curvature was suppressed and was excellent in strength and adhesiveness, and came to complete this invention.

That is, the present invention includes the following contents.

[1] A resin composition comprising (a) an elastomer having a polycarbonate structure in a molecule, (b) an epoxy resin, (c) an inorganic filler, (d) a phenoxy resin, and (e) a carbodiimide compound.

[2] The resin composition according to [1], wherein the content of the component (c) is 75% by mass to 95% by mass when the nonvolatile component of the resin composition is 100% by mass.

[3] The resin according to [1] or [2], wherein the content of the component (a) is 30% by mass to 85% by mass when the nonvolatile component of the resin composition excluding the component (c) is 100% by mass. composition.

[4] The resin composition according to any one of [1] to [3], wherein a cured product obtained by thermosetting the resin composition at 180°C for 1 hour has an elastic modulus at 23°C of 8 Gpa or more.

[5] (a) a structure in which the component is represented by a structure represented by the formula (1-a) and a structure represented by the formula (1-b);

Formula (1-a)

Formula (1-b)

[In the above formula, R1 represents a residue excluding the hydroxyl group of the polycarbonate diol, R2 represents a residue excluding the carboxyl group or acid anhydride group of a polybasic acid or anhydride thereof, and R3 represents a residue other than the isocyanate group of the diisocyanate compound.]

The resin composition according to any one of [1] to [4], which is a resin having a

[6] The resin composition according to any one of [1] to [5], wherein the component (a) has a functional group capable of reacting with the component (b).

[7] The resin composition according to any one of [1] to [6], wherein the component (a) has a phenolic hydroxyl group.

[8] The resin composition according to any one of [1] to [7], further comprising (f) a curing agent, wherein the curing agent is at least one selected from phenol-based curing agents.

[9] The resin composition according to any one of [1] to [8], which is a resin composition for an insulating layer of a semiconductor chip package.

[10] A resin sheet having a support and a resin composition layer formed on the support and comprising the resin composition according to any one of [1] to [9].

[11] The resin sheet according to [10], which is a resin sheet for an insulating layer of a semiconductor chip package.

[12] A circuit board comprising an insulating layer formed of a cured product of the resin composition according to any one of [1] to [9].

[13] A semiconductor chip package in which a semiconductor chip is mounted on the circuit board according to [12].

[14] A semiconductor chip package comprising a semiconductor chip sealed with the resin composition according to any one of [1] to [9], or the resin sheet according to [10].

ADVANTAGE OF THE INVENTION According to this invention, curvature is suppressed and the resin composition from which the hardened|cured material (insulating layer) excellent in strength and adhesiveness is obtained; A resin sheet, a circuit board, and a semiconductor chip package using the same can be provided.

Hereinafter, the resin composition, the resin sheet, the circuit board, and the semiconductor chip package of this invention are demonstrated in detail.

[resin composition]

The resin composition of the present invention contains (a) an elastomer having a polycarbonate structure in a molecule, (b) an epoxy resin, (c) an inorganic filler, (d) a phenoxy resin, and (e) a carbodiimide compound. If necessary, it may further include (f) a curing agent, (g) a curing accelerator, and (h) a flame retardant. Hereinafter, each component included in the resin composition will be described in detail.

<(a) Elastomer having a polycarbonate structure in the molecule>

The resin composition of the present invention includes (a) an elastomer having a polycarbonate structure in a molecule. By including a flexible resin like the component (a), an insulating layer having excellent insulation reliability, suppressing the occurrence of warpage, and having a low coefficient of linear thermal expansion can be obtained.

In the present invention, the elastomer is preferably a resin having rubber elasticity, or a resin exhibiting rubber elasticity by polymerization or solidification. As rubber elasticity, for example, in conformity with Japanese Industrial Standards (JIS K7 161), when a tensile test is performed at a temperature of 25°C and a humidity of 40% RH, a resin exhibiting an elastic modulus of 1 GPa or less is preferable.

From the viewpoint of suppressing warpage, the elastomer of the component (a) is preferably at least one resin selected from a resin having a glass transition temperature (Tg) of 25°C or lower and a liquid resin at 25°C.

The glass transition temperature of resin whose glass transition temperature (Tg) is 25 degrees C or less becomes like this. Preferably it is 20 degrees C or less, More preferably, it is 15 degrees C or less. Although the lower limit of a glass transition temperature is not specifically limited, Usually, it can be made into -15 degreeC or more. Moreover, as resin which is liquid at 25 degreeC, Preferably it is resin which is liquid at 20 degrees C or less, More preferably, it is resin which is liquid at 15 degrees C or less.

As one preferred embodiment of the component (a), a structure represented by the formula (1-a) (urethane and polycarbonate structures; ) (imide structure, hereinafter may be abbreviated as "structure (1-b)" in some cases).

Formula (1-a)

Formula (1-b)

[In the above formula, R1 represents a residue excluding the hydroxyl group of the polycarbonate diol, R2 represents a residue excluding the carboxyl group or acid anhydride group of a polybasic acid or anhydride thereof, and R3 represents a residue other than the isocyanate group of the diisocyanate compound.]

In addition, the terminus of the above formula indicates a bonding position, not a methyl group. The same is true for other chemical formulas.

The number average molecular weight of the polycarbonate diol is preferably 500 to 5,000, more preferably 1,000 to 3,000 from the viewpoint of the flexibility of the cured product of the resin composition and the solvent solubility of the component (A). The hydroxyl equivalent of the polycarbonate diol is preferably 250 to 1,250, more preferably 500 to 1,000, from the viewpoint of flexibility of the cured product of the resin composition and chemical resistance.

Examples of the diisocyanate compound include aromatic diisocyanates such as toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, xylylene diisocyanate and diphenylmethane diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate; Alicyclic diisocyanate, such as isophorone diisocyanate, is mentioned. Among these, aromatic diisocyanate is preferable, and toluene-2,4-diisocyanate is more preferable.

Examples of the polybasic acid or anhydride thereof include pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, naphthalenetetracarboxylic acid, 5-(2,5-dioxotetrahydrofuryl)-3- tetrabasic acids such as methyl-cyclohexene-1,2-dicarboxylic acid and 3,3'-4,4'-diphenylsulfonetetracarboxylic acid and anhydrides thereof, trimellitic acid, cyclohexanetricarboxyl Tribasic acids such as acids and anhydrides thereof, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho (1, 2-C) furan-1,3-dione; and the like. Among these, tetrabasic acid anhydride is preferable, tetrabasic acid dianhydride is more preferable, and benzophenonetetracarboxylic dianhydride is still more preferable.

R 1 is preferably of formula (1-c):

Formula (1-c)

[In the above formula, each of k+1 R 4 independently represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, and k represents an integer of 5 to 30.]

It is a divalent group represented by .

The alkylene group for R4 may be linear or branched. Examples of the substituent which the alkylene group of R4 may have include a halogen atom, a cycloalkyl group having 4 to 8 carbon atoms, and an aryl group having 6 to 14 carbon atoms. It is preferable that the alkylene group of R4 is unsubstituted.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the cycloalkyl group having 4 to 8 carbon atoms include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.

Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, and 9-anthryl group.

Each of k+1 pieces of R 4 is independently an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 2 to 18 carbon atoms, still more preferably an alkylene group having 3 to 16 carbon atoms. k is an integer of preferably 5 to 25, more preferably an integer of 5 to 20.

R2 is preferably of the formula:

[In the above formula, A is an oxygen atom, a sulfur atom, CO, SO, SO ₂ , CH ₂ , CH(CH ₃ ), C(CH ₃ ) ₂ , C(CF ₃ ) ₂ , or C(CCl ₃ ) ₂ indicates In the above formula, the hydrogen atom bonded to the carbon atom may be substituted with a substituent selected from a halogen atom and an alkyl group having 1 to 8 carbon atoms.]

at least one selected from the group of tetravalent groups represented by any one of them.

Among R2 (tetravalent group) represented by the above formula, a tetravalent group having an aromatic ring is preferable, and a tetravalent group having two or more aromatic rings is more preferable, and the following formula:

[In the above formula, A is an oxygen atom, a sulfur atom, CO, SO, SO ₂ , CH ₂ , CH(CH ₃ ), C(CH ₃ ) ₂ , C(CF ₃ ) ₂ , or C(CCl ₃ ) ₂ indicates In the above formula, the hydrogen atom bonded to the carbon atom may be substituted with a substituent selected from a halogen atom and an alkyl group having 1 to 8 carbon atoms.]

The tetravalent group represented by is most preferred.

A is preferably CO.

A hydrogen atom bonded to a carbon atom in the above formula (ie, a hydrogen atom bonded to a carbon atom in the tetravalent group represented by R 2 ) may be substituted with a substituent selected from a halogen atom and an alkyl group having 1 to 8 carbon atoms. It is preferable that the said hydrogen atom is not substituted.

As a halogen atom, the thing mentioned above is mentioned.

The alkyl group may be linear or branched. Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1 -Ethylpropyl group, hexyl group, isohexyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, and octyl group are mentioned. .

R3 is preferably of the formula:

[In the above formula, the hydrogen atom bonded to the carbon atom may be substituted with a substituent selected from a halogen atom and an alkyl group having 1 to 8 carbon atoms.]

at least one selected from the group of the divalent group represented by any one of them. In addition, the terminus of the above formula indicates a bonding position, not a methyl group. For example, the end of the formula indicates a hexamethylene group, not an octane.

A hydrogen atom bonded to a carbon atom in the formula (ie, a hydrogen atom bonded to a carbon atom in the divalent group of R 3 ) is a substituent selected from a halogen atom and an alkyl group having 1 to 8 carbon atoms (preferably 1 to 8 carbon atoms). of an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms, and most preferably a methyl group).

Examples of the halogen atom and the alkyl group having 1 to 8 carbon atoms include those described above. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1 -Ethylpropyl group, hexyl group, isohexyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, and 2-ethylbutyl group are mentioned.

Among R3 (divalent group) represented by the above formula, a divalent group having an aromatic ring or an alicyclic ring is preferable, and a divalent organic group having an alicyclic ring is more preferable. In the case of a divalent group having an aromatic ring, the formula:

[In the above formula, the hydrogen atom bonded to the carbon atom may be substituted with an alkyl group having 1 to 8 carbon atoms (preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group).]

A divalent group represented by any one of them is preferable, and a 4-methyl-1,3-phenylene group (ie, a residue excluding the isocyanate group of toluene-2,4-diisocyanate) is particularly preferable.

As (a) component, it is preferable to have a functional group which can react with (b) component mentioned later.

In one suitable embodiment, the functional group capable of reacting with component (b) is selected from the group consisting of a hydroxyl group (more preferably a phenolic hydroxyl group), a carboxy group, an acid anhydride group, an amino group, an epoxy group, an isocyanate group and a urethane group. It is one or more types of functional groups selected. Especially, as said functional group, a hydroxyl group, an acid anhydride group, an epoxy group, and an isocyanate group are preferable, and a hydroxyl group, an acid anhydride group, and an epoxy group are more preferable.

The number average molecular weight (Mn) is preferably 1,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 7,500 to 30,000, still more preferably 10,000 to 15,000. Here, the number average molecular weight (Mn) of resin is a polystyrene conversion number average molecular weight measured using GPC (gel permeation chromatography).

The functional group equivalent in the case of having a functional group becomes like this. Preferably it is 100-10000, More preferably, it is 200-5000. In addition, a functional group equivalent is the number of grams of resin containing 1 gram equivalent of a functional group. For example, the epoxy group equivalent can be measured according to JISK7236. The hydroxyl equivalent can be calculated by dividing the molecular weight of KOH by the hydroxyl value measured according to JIS K1557-1.

As one preferred embodiment of the component (a), a polycarbonate resin having a glass transition temperature of 25° C. or less is preferable, a polycarbonate resin containing a hydroxyl group (more preferably a polycarbonate resin containing a phenolic hydroxyl group), a polycarbonate containing a carboxy group At least one resin selected from the group consisting of a carbonate resin, an acid anhydride group-containing polycarbonate resin, an epoxy group-containing polycarbonate resin, an isocyanate group-containing polycarbonate resin and a urethane group-containing polycarbonate resin is preferable. Here, "polycarbonate resin" refers to resin containing a polycarbonate structure, and in these resins, the polycarbonate structure may be contained in the main chain or may be contained in the side chain.

The content of the component (a) in the resin composition is preferably 85% by mass or less, more preferably 80% by mass, when the nonvolatile component of the resin composition excluding the component (c) is 100% by mass from the viewpoint of imparting flexibility. Hereinafter, more preferably, it is 75 mass % or less, More preferably, it is 73 mass % or less. The lower limit is preferably 30% by mass or more, more preferably 35% by mass or more, still more preferably 45% by mass or more, still more preferably 55% by mass or more.

<(b) Epoxy resin>

The resin composition contains an epoxy resin. Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolak type epoxy Resin, phenol novolak type epoxy resin, alicyclic epoxy resin having an ester skeleton, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, Glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, butadiene structure epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclo A hexane dimethanol type epoxy resin, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin, a tetraphenylethane type epoxy resin, etc. are mentioned. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

It is preferable that the epoxy resin contains the epoxy resin which has two or more epoxy groups in 1 molecule. When the nonvolatile component of the epoxy resin is 100 mass %, it is preferable that at least 50 mass % or more is an epoxy resin which has two or more epoxy groups in 1 molecule. Among them, an epoxy resin that has two or more epoxy groups in one molecule and is liquid at a temperature of 20°C (hereinafter referred to as “liquid epoxy resin”), and has three or more epoxy groups in one molecule, and is a solid epoxy at a temperature of 20°C It is preferable to include a resin (hereinafter referred to as "solid epoxy resin"). As the epoxy resin, a resin composition having excellent flexibility is obtained by using a liquid epoxy resin and a solid epoxy resin together. Moreover, the breaking strength of the hardened|cured material of a resin composition also improves.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin having an aromatic structure, and glycidylamine type epoxy resin having aromatic structure. Resin, a phenol novolak-type epoxy resin, an alicyclic epoxy resin having an ester skeleton having an aromatic structure, a cyclohexanedimethanol-type epoxy resin having an aromatic structure, and an epoxy resin having a butadiene structure having an aromatic structure are preferable, and bisphenol A A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, and a naphthalene type epoxy resin are more preferable, and a bisphenol A type epoxy resin and a bisphenol F type epoxy resin are still more preferable. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC, "828US" manufactured by Mitsubishi Chemical Corporation, "jER828EL" (bisphenol A type epoxy resin), " JER806", "jER807" (bisphenol F-type epoxy resin), "jER152" (phenol novolak-type epoxy resin), "630", "630LSD" (aminophenol-type epoxy resin), " ZX1059" (mixture of bisphenol A epoxy resin and bisphenol F epoxy resin), "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase Chemtex, "Celoxide 2021P" manufactured by Daicel ( The alicyclic epoxy resin which has an ester skeleton), "ZX1658" by a Nippon-Chemical company, "ZX1658GS" (liquid 1, 4- glycidyl cyclohexane) is mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Content of the liquid epoxy resin in the resin composition, when the non-volatile component in the resin composition is 100 mass %, from the viewpoint of improving the compatibility of the component (a), preferably 1 mass % or more, more preferably 2 It is mass % or more, More preferably, it is 2.5 mass % or more. Although the upper limit of content of an epoxy resin is not specifically limited as long as the effect of this invention is shown, Preferably it is 15 mass % or less, More preferably, it is 10 mass % or less, More preferably, it is 5 mass % or less.

The epoxy equivalent of the liquid epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, still more preferably 110 to 1000. By being in this range, the crosslinking density of the hardened|cured material of a resin composition becomes sufficient, and when using hardened|cured material as an insulating layer, the insulating layer with a small surface roughness can be brought. In addition, the epoxy equivalent of a liquid epoxy resin can be measured according to JISK7236, It is the mass of resin containing 1 equivalent of an epoxy group.

The weight average molecular weight of a liquid epoxy resin becomes like this. Preferably it is 100-5000, More preferably, it is 250-3000, More preferably, it is 400-1500. Here, the weight average molecular weight of a liquid epoxy resin is the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography (GPC) method.

Examples of the solid-state epoxy resin include a naphthalene-type tetrafunctional epoxy resin, a cresol novolak-type epoxy resin, a dicyclopentadiene-type epoxy resin having an aromatic structure, a trisphenol-type epoxy resin, a naphthol-type epoxy resin, a biphenyl-type epoxy resin, and naphthylene. Ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferable, naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, and biphenyl type epoxy resin , a naphthylene ether type epoxy resin is more preferable, and a naphthalene type tetrafunctional epoxy resin and a naphthylene ether type epoxy resin are still more preferable. As a specific example of a solid-state epoxy resin, "HP4032H" (naphthalene type epoxy resin) manufactured by DIC, "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), "N-690" (cresol novolak type) Epoxy resin), “N-695” (cresol novolak type epoxy resin), “HP-7200”, “HP-7200L”, “HP-7200HH”, “HP-7200H”, “HP-7200HHH” (dicyclo Pentadiene type epoxy resin), "EXA7311", "EXA7311-G3", "EXA7311-G4", "EXA7311-G4S", "HP6000" (naphthylene ether type epoxy resin), "EPPN-502H" manufactured by Nippon Kayaku ” (trisphenol-type epoxy resin), “NC7000L” (naphthol novolac-type epoxy resin), “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl-type epoxy resin), New Nittetsu Sumikin Chemical "ESN475V" (naphthol type epoxy resin), "ESN485" (naphthol novolak type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (vixyle Nol-type epoxy resin), "YL7760" (bisphenol AF-type epoxy resin), "YX8800" (anthracene-type epoxy resin), "PG-100" by Osaka Gas Chemicals, "CG-500", " YL7800" (fluorene type epoxy resin), "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1031S" (tetraphenylethane type epoxy resin), "157S70" (bisphenol novolak type epoxy resin) , Mitsubishi Chemical Corporation "YX4000HK" (bixylenol type epoxy resin), "YX8800" (anthracene type epoxy resin), Osaka Gas Chemical Company "PG-100", "CG-500", Mitsubishi Chemical Corporation "YL7800" (fluorene type epoxy resin), "jER1031S" by Mitsubishi Chemical Corporation (tetraphenylethane type epoxy resin), etc. are mentioned. These may be used individually by 1 type, and can be used in combination of 2 or more type.

When content of the solid-state epoxy resin in a resin composition makes the nonvolatile component in a resin composition 100 mass %, from a viewpoint of adjusting the viscosity of a resin composition, Preferably it is 0.1 mass % or more, More preferably, it is 0.2 mass % or more. , More preferably, it is 0.3 mass % or more. Although the upper limit of content of an epoxy resin is not specifically limited as long as the effect of this invention is shown, Preferably it is 10 mass % or less, More preferably, it is 5 mass % or less, More preferably, it is 1 mass % or less.

The epoxy equivalent of a solid epoxy resin becomes like this. Preferably it is 50-5000, More preferably, it is 50-3000, More preferably, it is 80-2000, More preferably, it is 110-1000. By being in this range, the crosslinking density of hardened|cured material becomes sufficient and it can bring about the insulating layer with small surface roughness. In addition, the epoxy equivalent of a solid-state epoxy resin can be measured according to JISK7236, It is the mass of resin containing 1 equivalent of an epoxy group.

The weight average molecular weight of a solid epoxy resin becomes like this. Preferably it is 100-5000, More preferably, it is 250-3000, More preferably, it is 400-1500. Here, the weight average molecular weight of a solid-state epoxy resin is the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography (GPC) method.

When the content of the liquid epoxy resin is B1 (mass %) and the content of the solid epoxy resin is B2 (mass %), it is preferable to satisfy the relationship of B1 > B2 from the viewpoint of adjusting the melt viscosity. The difference between B1 and B2 (B1-B2) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.3% by mass or more, 0.5% by mass or more, or 1% by mass or more. am. Although the upper limit of the difference (B1-B2) is not specifically limited, Usually, it can be 10 mass % or less, 5 mass % or less, etc.

The amount ratio (solid epoxy resin/liquid epoxy resin) of a liquid epoxy resin and a solid epoxy resin is mass ratio, and the range of 0.01-1 is preferable. By making the amount ratio of the liquid epoxy resin and the solid epoxy resin within this range, i) when used in the form of a resin sheet, adequate adhesion can be brought, and ii) when used in the form of a resin sheet, sufficient flexibility is obtained, , handling is improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects of i) to iii), the amount ratio of the liquid epoxy resin and the solid epoxy resin (solid epoxy resin/liquid epoxy resin) is more preferably in the range of 0.05 to 0.8 by mass ratio, and more preferably in the range of 0.1 to 0.5 desirable.

<(c) Inorganic filler>

The resin composition contains (c) an inorganic filler. Although the material of the inorganic filler is not particularly limited, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, Aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate , barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica or alumina is suitable, and silica is especially suitable. Moreover, as a silica, spherical silica is preferable. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

The average particle diameter of the inorganic filler is preferably 5 µm or less, more preferably 2.5 µm or less, still more preferably 2.2 µm or less, more preferably from the viewpoint of improving circuit embedding properties and obtaining an insulating layer with low surface roughness. It is preferably 2 μm or less. Although the lower limit of the said average particle diameter is not specifically limited, Preferably it is 0.01 micrometer or more, More preferably, it is 0.05 micrometer or more, More preferably, it is 0.1 micrometer or more. As a commercial item of the inorganic filler which has such an average particle diameter, "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Adomatex Corporation, "UFP-30" manufactured by Denki Chemical Co., Ltd., Toku, for example, "Silver NSS-3N", "Silver NSS-4N", "Silver NSS-5N" manufactured by Yama Corporation, "SC2500SQ", "SO-C6", "SO-C4", "SO-C2" manufactured by Adomatex , "SO-C1", etc. are mentioned.

The average particle diameter of the inorganic filler can be measured by a laser diffraction/scattering method based on the Mie scattering theory. Specifically, it can measure by creating the particle size distribution of an inorganic filler on a volume basis with a laser diffraction scattering type particle size distribution measuring apparatus, and making the intermediate diameter into an average particle diameter. As a measurement sample, what disperse|distributed the inorganic filler in water by ultrasonic wave can be used preferably. As a laser diffraction scattering type particle size distribution analyzer, "LA-500" by Horiba Corporation, etc. can be used.

From the viewpoint of improving moisture resistance and dispersibility, the inorganic filler is an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, an alkoxysilane compound, an organosilazane compound, and a titanate-based coupler. It is preferable that it is processed with 1 or more types of surface treatment agents, such as a ring agent. As a commercial item of a surface treatment agent, Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidoxypropyl trimethoxysilane), Shin-Etsu Chemical Co., Ltd. make "KBM803" (3-mercaptopropyl trimethoxysilane), for example, ), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. “SZ-31” (hexamethyldisilazane) manufactured by Kyoko Co., Ltd. “KBM103” (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. “KBM-4803” manufactured by Shin-Etsu Chemical Co., Ltd. (long-chain epoxy type silane coupling agent) ) and the like.

The grade of the surface treatment by a surface treating agent can be evaluated according to the carbon amount per unit surface area of an inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, and still more preferably 0.2 mg/m 2 or more. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin varnish or melt viscosity in sheet form, 1 mg/m2 or less is preferable, 0.8 mg/m2 or less is more preferable, and 0.5 mg/m2 or less is still more preferable. .

The amount of carbon per unit surface area of an inorganic filler can be measured, after washing-processing the inorganic filler after surface treatment with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, followed by ultrasonic cleaning at 25° C. for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" by Horiba Corporation, etc. can be used.

As for content of the inorganic filler in a resin composition, 75 mass % - 95 mass % are preferable. Preferably it is 78 mass % or more, More preferably, it is 80 mass % or more, More preferably, it is 83 mass % or more. The upper limit is preferably 90% by mass or less from the viewpoint of mechanical strength of the insulating layer, particularly elongation.

<(d) phenoxy resin>

The resin composition of this invention contains a phenoxy resin as (d) component.

From the viewpoint of obtaining a good insulating layer of mechanical strength, the weight average molecular weight of the phenoxy resin is preferably 10000 or more, more preferably 15000 or more, still more preferably 20000 or more, even more preferably 25000 or 30000 or more. . From a viewpoint of obtaining good compatibility, the upper limit of the weight average molecular weight of a thermoplastic resin becomes like this. Preferably it is 200000 or less, More preferably, it is 180000 or less, More preferably, it is 160000 or less, More preferably, it is 150000 or less. The weight average molecular weight of a thermoplastic resin can be measured by the gel permeation chromatography (GPC) method, for example. Specifically, the weight average molecular weight (in terms of polystyrene) of the thermoplastic resin was measured using LC-9A/RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P/K- manufactured by Showa Denko Corporation as a column. 804L/K-804L can be measured using chloroform etc. as a mobile phase at a column temperature of 40 degreeC, and can be calculated using the standard polystyrene calibration curve.

In combination with (a) an elastomer having a polycarbonate structure in the molecule, (b) an epoxy resin, (c) an inorganic filler, and (e) a carbodiimide compound, from the viewpoint of obtaining strength and adhesion, particularly excellent adhesion From the viewpoint of obtaining, the thermoplastic resin preferably has at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom or a functional group containing a carbon-carbon double bond. Examples of such functional groups include a hydroxyl group, a carboxyl group, an acid anhydride group, an epoxy group, an amino group, a thiol group, an enol group, an enamine group, a urea group, a cyanate group, an isocyanate group, a thioisocyanate group, a diimide group, an alkenyl group, an allene group and a ketene group. and at least one selected from the group consisting of groups. As the acid anhydride group, a carboxylic acid anhydride group is preferable. Suitable examples of the alkenyl group include a vinyl group, an allyl group, and a styryl group. By using a thermoplastic resin having such a functional group, the glass transition temperature of the insulating layer obtained tends to be high, and an insulating layer exhibiting good heat resistance can be realized. When the thermoplastic resin contains such a functional group, the functional group equivalent of the thermoplastic resin is preferably 100000 or less, more preferably 90000 or less, 80000 or less, 70000 or less, 60000 or less, 50000 or less, 40000 or less, 30000 or less, 20000 or less, 10000 or less, 8000 or less, 6000 or less, or 5000 or less. Although the lower limit of the said functional group equivalent is not specifically limited, Usually, it can be set as 50 or more, 100 or more, etc.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton , phenoxy resins having at least one skeleton selected from the group consisting of anthracene skeleton, adamantane skeleton, terpene skeleton and trimethylcyclohexane skeleton. Any one functional group, such as a phenolic hydroxyl group and an epoxy group, may be sufficient as the terminal of a phenoxy resin. Specific examples of the phenoxy resin include "1256" and "4250" (both bisphenol A skeleton-containing phenoxy resins) manufactured by Mitsubishi Chemical Co., Ltd., "YX8100" (bisphenol S skeleton-containing phenoxy resin) and "YX6954" (bisphenol acetophenone skeleton-containing phenoxy resin), and in addition, "FX280" and "FX293" manufactured by Shin-Nittetsu Sumikin Chemical Co., Ltd., "YL7553", "YL6794" manufactured by Mitsubishi Chemical Co., Ltd., "YL6794", "YL7213", "YL7290", "YL7482", etc. are mentioned.

<(e) carbodiimide compound>

The resin composition of the present invention contains a carbodiimide compound as component (e).

The carbodiimide compound is a compound having one or more carbodiimide groups (-N=C=N-) in one molecule, and (a) an elastomer having a polycarbonate structure in the molecule, (b) an epoxy resin; By using in combination with (c) an inorganic filler and (d) a phenoxy resin, an insulating layer excellent in strength and adhesiveness can be obtained. As a carbodiimide compound, the compound which has two or more carbodiimide groups in 1 molecule is preferable. A carbodiimide compound may be used individually by 1 type, and may be used in combination of 2 or more type.

In one embodiment, the carbodiimide compound contained in the resin composition of the present invention contains a structural unit represented by the following formula (2).

Formula (2)

(In the formula (2), X represents an alkylene group, a cycloalkylene group or an arylene group, which may have a substituent. p represents an integer of 1 to 5. When there are two or more X's, they are the same They may be different from each other. * indicates the number of bonds.)

The number of carbon atoms in the alkylene group represented by X is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 6, 1-4, or 1-3. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Suitable examples of the alkylene group include a methylene group, an ethylene group, a propylene group, and a butylene group.

The number of carbon atoms in the cycloalkylene group represented by X is preferably 3 to 20, more preferably 3 to 12, still more preferably 3 to 6. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Suitable examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group.

The arylene group represented by X is a group obtained by removing two hydrogen atoms on an aromatic ring from an aromatic hydrocarbon. The number of carbon atoms in the arylene group is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, still more preferably 6 to 10. The number of carbon atoms of the substituent is not included in the number of carbon atoms. A phenylene group, a naphthylene group, and an anthracenylene group are mentioned as a suitable example of the said arylene group.

In the combination of (a) an elastomer having a polycarbonate structure in the molecule, (b) an epoxy resin, (c) an inorganic filler, and (d) a phenoxy resin, from the viewpoint of realizing an insulating layer having further excellent strength and adhesion, It is preferable that X is an alkylene group or a cycloalkylene group, and these may have a substituent.

The alkylene group, cycloalkylene group or arylene group represented by X may have a substituent. Although it does not specifically limit as said substituent, For example, a halogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkyloxy group, an aryl group, an aryloxy group, an acyl group, and an acyloxy group are mentioned. As a halogen atom used as a substituent, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example. The alkyl group and alkoxy group used as the substituent may be linear or branched, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 6, 1 to 4 , or 1 to 3. The number of carbon atoms in the cycloalkyl group or cycloalkyloxy group used as the substituent is preferably 3 to 20, more preferably 3 to 12, still more preferably 3 to 6. The aryl group used as a substituent is a group obtained by excluding one hydrogen atom on an aromatic ring from an aromatic hydrocarbon, and the number of carbon atoms is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, even more preferably 6 to 10. The number of carbon atoms in the aryloxy group used as the substituent is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, still more preferably 6 to 10. The acyl group used as the substituent refers to a group represented by the formula: -C(=O)-R1 (in the formula, R1 represents an alkyl group or an aryl group). The alkyl group represented by R1 may be linear or branched, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 6, 1 to 4, or 1 to 3. The number of carbon atoms in the aryl group represented by R1 is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, even more preferably 6 to 10. The acyloxy group used as a substituent refers to a group represented by the formula: -O-C(=O)-R1 (in the formula, R1 has the same meaning as above). Especially, as a substituent, an alkyl group, an alkoxy group, and an acyloxy group are preferable, and an alkyl group is more preferable.

In general formula (2), p represents the integer of 1-5. In the combination of (a) an elastomer having a polycarbonate structure in a molecule, (b) an epoxy resin, (c) an inorganic filler, and (d) a phenoxy resin, from the viewpoint of realizing an insulating layer having further excellent strength and adhesion, p is preferably 1 to 4, more preferably 2 to 4, still more preferably 2 or 3.

In general formula (2), when two or more X exist, they may be same or different. In one suitable embodiment, at least one X is an alkylene group or a cycloalkylene group, which may have a substituent.

In one suitable embodiment, the carbodiimide compound is preferably 50 mass % or more, more preferably 60 mass % or more, still more preferably when the mass of the entire molecule of the carbodiimide compound is 100 mass %. contains 70 mass % or more, more preferably 80 mass % or more, or 90 mass % or more, and contains the structural unit represented by Formula (2). The carbodiimide compound may be substantially composed of a structural unit represented by the general formula (2) except for the terminal structure. Although it does not specifically limit as a terminal structure of a carbodiimide compound, For example, an alkyl group, a cycloalkyl group, and an aryl group are mentioned, These may have a substituent. The alkyl group, cycloalkyl group, and aryl group used as the terminal structure may be the same as the alkyl group, cycloalkyl group, and aryl group described for the substituents that the group represented by X may have. In addition, the substituent which group used as terminal structure may have may be the same as the substituent which group represented by X may have.

From a viewpoint of being able to suppress generation|occurrence|production of the outgas at the time of hardening a resin composition, the weight average molecular weight of a carbodiimide compound becomes like this. Preferably it is 500 or more, More preferably, it is 600 or more, More preferably, it is 700 or more. More preferably, it is 800 or more, Especially preferably, it is 900 or more or 1000 or more. In addition, from the viewpoint of obtaining good compatibility, the upper limit of the weight average molecular weight of the carbodiimide compound is preferably 5000 or less, more preferably 4500 or less, still more preferably 4000 or less, even more preferably 3500 or less, Especially preferably, it is 3000 or less. The weight average molecular weight of the carbodiimide compound can be measured, for example, by a gel permeation chromatography (GPC) method (in terms of polystyrene).

In addition, the carbodiimide compound may contain an isocyanate group (-N=C=O) in a molecule|numerator derived from the manufacturing method. The content of isocyanate groups in the carbodiimide compound (also referred to as “NCO content”) is preferably 5 It is mass % or less, More preferably, it is 4 mass % or less, More preferably, it is 3 mass % or less, More preferably, it is 2 mass % or less, Especially preferably, it is 1 mass % or less or 0.5 mass % or less.

As the carbodiimide compound, a commercially available product may be used. Commercially available carbodiimide compounds include, for example, Nisshinbo Chemical Co., Ltd. Carbodilite (registered trademark) V-02B, V-03, V-04K, V-07 and V-09; Staverkuzol (registered trademark) P, P400, and Hicardil 510 are mentioned.

In combination with (a) an elastomer having a polycarbonate structure in the molecule, (b) an epoxy resin, (c) an inorganic filler, and (d) a phenoxy resin, to obtain an insulating layer excellent in any properties of strength and adhesion From a viewpoint, the content of the carbodiimide compound in the resin composition is preferably 1 mass % or more, more preferably 2 mass % or more, and still more preferably 3 mass % or more, 4 mass % or more, or 5 mass % or more. Although the upper limit of content of a carbodiimide compound is not specifically limited, 30 mass % or less is preferable, 20 mass % or less is more preferable, 15 mass % or less is still more preferable.

<(f) curing agent>

The resin composition may include (f) a curing agent. The curing agent is not particularly limited as long as it has a function of curing the resin such as component (b), and for example, a phenol-based curing agent (including a naphthol-based curing agent), an active ester-based curing agent, a benzoxazine-based curing agent, and cyanate An ester-type hardening|curing agent etc. are mentioned. A hardening|curing agent may be used individually by 1 type, or may use 2 or more types together. (d) component is preferably at least one selected from a phenol-based curing agent, an active ester-based curing agent and a cyanate ester-based curing agent, preferably at least one selected from a phenol-based curing agent and an active ester-based curing agent, and a phenol-based curing agent It is more preferable that it is a hardening|curing agent.

As the phenol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoints of heat resistance and water resistance. Moreover, a nitrogen-containing phenolic hardening|curing agent is preferable from an adhesive viewpoint with a wiring layer, and a triazine skeleton containing phenolic hardening|curing agent is more preferable. Among them, a triazine skeleton-containing phenol novolac curing agent is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to a wiring layer.

As a specific example of a phenolic hardening|curing agent, "MEH-7700", "MEH-7810", "MEH-7851" by Meiwa Kasei Corporation, "NHN", "CBN", "GPH" by Nippon Kayaku, "GPH", Shin-Nitetsu "SN170", "SN180", "SN190", "SN475", "SN485", "SN495V", "SN375", "SN395" manufactured by Sumikin, "TD-2090", "LA-7052" manufactured by DIC Corporation ”, “LA-7054”, “LA-1356”, “LA-3018-50P”, “EXB-9500”, “HPC-9500”, “KA-1160”, “KA-1163”, “KA-1165” ", "GDP-6115L", "GDP-6115H" by Gunei Chemical Co., Ltd., "OPE-1000" by Mitsubishi Gas Chemical Co., Ltd., etc. are mentioned.

From the viewpoint of obtaining an insulating layer excellent in adhesion to the wiring layer, an active ester curing agent is also preferable. Although there is no restriction|limiting in particular as an active ester-type hardening|curing agent, Generally, ester groups with high reaction activity, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxy compound esters, are two per molecule. The compounds having the above are preferably used. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound, a phenol compound and/or a naphthol compound is more preferable. . Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, and m-cresol. , p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, tri Hydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolak, etc. are mentioned. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol to one molecule of dicyclopentadiene.

Specifically, an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoyl product of phenol novolac An ester compound is preferable, and among these, the active ester compound containing a naphthalene structure, and the active ester compound containing a dicyclopentadiene type diphenol structure are more preferable. "Dicyclopentadiene-type diphenol structure" represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

Commercially available active ester curing agents are active ester compounds containing a dicyclopentadiene-type diphenol structure, such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM" ", "EXB-8000L-65TM" (manufactured by DIC), "EXB9416-70BK" (manufactured by DIC) as an active ester compound containing a naphthalene structure, and "DC808" as an active ester compound containing an acetylated product of phenol novolac ” (manufactured by Mitsubishi Chemical Corporation), “YLH1026” (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoyl product of phenol novolac, and “DC808” (Mitsubishi Chemical Corporation) as an active ester curing agent that is an acetylated product of phenol novolac manufacture), "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation) etc. are mentioned as an active ester type hardening|curing agent which is a benzoyl product of phenol novolak.

As a specific example of a benzoxazine type hardening|curing agent, "HFB2006M" by Showa Kobunshi, "P-d" by Shikoku Kasei Co., Ltd., and "F-a" are mentioned.

Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), and 4,4'-methylenebis(2,6-dimethyl). Phenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cya) natephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanate) Bifunctional cyanate resins such as phenyl)thioether and bis(4-cyanatephenyl)ether; Polymer etc. are mentioned. As a specific example of a cyanate ester type hardening|curing agent, "PT30" and "PT60" (all are phenol novolak-type polyfunctional cyanate ester resin), "BA230", "BA230S75" (a part of bisphenol A dicyanate by Ronza Japan) Or all of it is triazine-ized, and a trimer is a prepolymer) etc. are mentioned.

When the resin composition contains component (d), the content of the curing agent in the resin composition is not particularly limited, but is preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 5% by mass or less. . Moreover, although there is no restriction|limiting in particular as for a minimum, 1 mass % or more is preferable.

<(g) curing accelerator>

The resin composition may include (g) a curing accelerator. Examples of the curing accelerator include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, and a metal-based curing accelerator, and a phosphorus-based curing accelerator, an amine-based curing accelerator, and an imidazole-based curing accelerator. , metal-based curing accelerators are preferable, and amine-based curing accelerators, imidazole-based curing accelerators and metal-based curing accelerators are more preferable. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the phosphorus-based curing accelerator include triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphine. Phonium thiocyanate, tetraphenyl phosphonium thiocyanate, butyl triphenyl phosphonium thiocyanate, etc. are mentioned, Triphenyl phosphine and tetrabutyl phosphonium decanoate are preferable.

Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8- and diazabicyclo(5,4,0)-undecene, and 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene are preferable.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl. Midazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole Sol, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl- 4-Methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2 phenylimidazolium trimelli Tate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimida Zolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-ethyl-4′-methylimidazolyl-(1′)]-ethyl-s-triazine , 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazineisocyanuric acid adduct, 2-phenylimidazoleisocyanuric acid adduct, 2- Phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benz Imidazole compounds such as imidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

A commercial item may be used as an imidazole-type hardening accelerator, For example, "P200-H50" by a Mitsubishi Chemical Company, etc. are mentioned.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, Trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]deca -5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1 -diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc. are mentioned, and dicyandiamide, 1 ,5,7-triazabicyclo[4.4.0]deca-5-ene is preferred.

As a metal type hardening accelerator, the organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, and a tin, is mentioned, for example. Specific examples of the organometallic complex include organocobalt complexes such as cobalt(II)acetylacetonate and cobalt(III)acetylacetonate, organocopper complexes such as copper(II)acetylacetonate, zinc(II)acetylacetonate, and the like. organic zinc complexes, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organometallic salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

When the resin composition contains the component (g), the content of the curing accelerator in the resin composition is not particularly limited, but when the total amount of the component (b) and the non-volatile component of the curing agent is 100% by mass, 0.01% by mass thru|or 3 mass % is preferable.

<(h) Flame Retardant>

The resin composition may include (h) a flame retardant. Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. A flame retardant may be used individually by 1 type, or may use 2 or more types together.

A commercial item may be used as a flame retardant, for example, "HCA-HQ" by Sanko Corporation, etc. are mentioned.

When the resin composition contains a flame retardant, the content of the flame retardant is not particularly limited, but preferably 0.5% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, still more preferably 0.5% by mass to 10 % by mass is more preferable.

<(i) optional additives>

The resin composition may further contain other additives as required. Examples of such other additives include organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds, and binders, thickeners, defoamers, and leveling agents. and resin additives such as adhesion-imparting agents and colorants.

<Physical properties of the resin composition>

The cured product obtained by thermosetting the resin composition of the present invention at 180°C for 1 hour has an elastic modulus at 23°C of 8 GPa or more. Although it does not specifically limit about an upper limit, For example, it can be 18 GPa or less, 15 GPa or less, 13 GPa or less, and 11 GPa or less. Generation|occurrence|production of the curvature of hardened|cured material can be suppressed by making an elasticity modulus into 8 GPa or more. The said elastic modulus can be measured according to the method as described in <Measurement of elastic modulus and tensile strength at break> mentioned later.

The cured product obtained by thermosetting the resin composition of the present invention at 180° C. for 1 hour has a breaking point strength (MPa) at 23° C. of 55 or more, preferably 60 or more, and more preferably 65 or more. Although it does not specifically limit about an upper limit, For example, it can be set as 100 or less. The said strength at break can be measured according to the method described in <Measurement of elastic modulus and tensile strength at break> mentioned later.

The resin composition of the present invention can bring a cured product (insulating layer) with suppressed warpage and excellent strength and adhesion, and by including the component (b), the compatibility of the component (a) is good. Therefore, the resin composition of the present invention is a resin composition for forming an insulating layer of a semiconductor chip package (resin composition for an insulating layer of a semiconductor chip package), a resin composition for forming an insulating layer of a circuit board (including a printed wiring board) ( A resin composition for forming an interlayer insulating layer on which a conductor layer is formed by plating, which can be suitably used as a resin composition for an insulating layer of a circuit board (resin for an interlayer insulating layer of a circuit board on which a conductor layer is formed by plating) composition) can be more suitably used.

Moreover, it can use suitably also as a resin composition for sealing a semiconductor chip (resin composition for semiconductor chip sealing), and a resin composition for forming wiring in a semiconductor chip (resin composition for semiconductor chip wiring formation).

[Resin Sheet]

The resin sheet of this invention consists of a support body and the resin composition layer joined with the said support body, and a resin composition layer consists of the resin composition of this invention.

The thickness of the resin composition layer is preferably 200 µm or less, more preferably 150 µm or less, still more preferably 100 µm or less, 80 µm or less, 60 µm or less, 50 µm or less, or 40 µm or less from the viewpoint of reducing the thickness. . Although the lower limit of the thickness of a resin composition layer is not specifically limited, Usually, it can be 1 micrometer or more, 5 micrometers or more, 10 micrometers or more.

Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable.

When a film made of a plastic material is used as the support, the plastic material is, for example, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyethylene naphthalate (hereinafter sometimes abbreviated as “PEN”). Polyester such as polyester, polycarbonate (hereinafter sometimes abbreviated as “PC”), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), poly Ether ketone, polyimide, etc. are mentioned. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When using metal foil as a support body, as metal foil, copper foil, aluminum foil, etc. are mentioned, for example, Copper foil is preferable. As the copper foil, a copper foil made of a single metal of copper may be used, or a foil made of an alloy of copper and another metal (eg, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) is used. also good

A support body may give a mat treatment and corona treatment to the surface to join with the resin composition layer.

Moreover, as a support body, you may use the support body with a mold release layer which has a mold release layer on the surface to join with a resin composition layer. As a mold release agent used for the mold release layer of a support body with a mold release layer, 1 or more types of mold release agents are mentioned from the group which consists of an alkyd resin, a polyolefin resin, a urethane resin, and a silicone resin, for example. A commercial item may be used for the support body with a release layer, for example, "SK-1", "AL-5", "AL-7" by Lintec which are PET film which has a release layer which has an alkyd resin type release agent as a main component. ', "Lumiror T60" by Toray Corporation, "Purex" by Teijin Corporation, "Uni-pil" by Unitica Corporation, etc. are mentioned.

Although it does not specifically limit as thickness of a support body, The range of 5 micrometers - 75 micrometers is preferable, and the range of 10 micrometers - 60 micrometers is more preferable. Moreover, when using a support body with a mold release layer, it is preferable that the thickness of the whole support body with a mold release layer is the said range.

The resin sheet can be produced by, for example, preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying this resin varnish to a support using a die coater or the like, and further drying to form a resin composition layer. .

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; cello carbitols such as sorb and butylcarbitol; aromatic hydrocarbons such as toluene and xylene; and amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

You may perform drying by well-known methods, such as heating and hot-air spraying. Although drying conditions are not specifically limited, Content of the organic solvent in a resin composition layer is 10 mass % or less, Preferably it is made to dry so that it may become 5 mass % or less. Although it changes with the boiling point of the organic solvent in a resin varnish, for example, when using the resin varnish containing 30 mass % - 60 mass % of an organic solvent, by drying at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes, the resin composition layer can be formed.

In the resin sheet, a protective film conforming to the support can be further laminated on the surface of the resin composition layer that is not bonded to the support (that is, the surface on the opposite side to the support). Although the thickness of a protective film is not specifically limited, For example, it is 1 micrometer - 40 micrometers. By laminating|stacking a protective film, adhesion of dust, etc. with respect to the surface of a resin composition layer, and a flaw can be prevented. The resin sheet can be wound and stored in a roll shape. When a resin sheet has a protective film, it becomes usable by peeling off a protective film.

Instead of the resin sheet of the present invention, a prepreg formed by impregnating a sheet-like fiber base material with the resin composition of the present invention may be used.

The sheet-like fiber base material used for the prepreg is not particularly limited, and those commonly used as the base material for prepregs, such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric, can be used. From a viewpoint of thickness reduction, the thickness of a sheet-like fiber base material becomes like this. Preferably it is 900 micrometers or less. Although the lower limit of the thickness of a sheet-like fiber base material is not specifically limited, Usually, it can be set as 1 micrometer or more.

A prepreg can be manufactured by well-known methods, such as a hot melt method and a solvent method.

The thickness of a prepreg can be made into the range same as the resin composition layer in the above-mentioned resin sheet.

The resin sheet of this invention can be used suitably in order to form an insulating layer in semiconductor chip package manufacture (resin sheet for insulation of a semiconductor chip package).

For example, the resin sheet of the present invention can be suitably used for forming an insulating layer of a circuit board (resin sheet for an insulating layer of a circuit board), and an interlayer insulating layer on which a conductor layer is formed by plating In order to form (for an interlayer insulating layer of a circuit board which forms a conductor layer by plating), it can use more suitably. Examples of the package using such a substrate include FC-CSP, MIS-BGA package, and ETS-BGA package.

Further, the resin sheet of the present invention can be suitably used for sealing a semiconductor chip (resin sheet for sealing semiconductor chip) or for forming wiring on a semiconductor chip (resin sheet for forming wiring on a semiconductor chip), for example, a Fan -Out type WLP (Wafer Level Package), Fan-in type WLP, Fan-out type PLP (Panel Level Package), Fan-in type PLP, etc. can be used appropriately. Moreover, it can be used suitably also for the MUF (Molding Under Filling) material etc. which are used after connecting a semiconductor chip to a board|substrate.

Furthermore, the resin sheet of this invention can be used suitably in order to form the insulating layer of circuit boards, such as another wide use which high insulation reliability is calculated|required, for example, printed wiring boards.

[circuit board]

The circuit board of this invention contains the insulating layer formed with the hardened|cured material of the resin composition of this invention.

The manufacturing method of the circuit board of this invention,

(1) a step of preparing a substrate with a wiring layer having a substrate and a wiring layer formed on at least one surface of the substrate;

(2) a step of laminating the resin sheet of the present invention on a substrate with a wiring layer so that the wiring layer is embedded in the resin composition layer, and thermosetting to form an insulating layer;

(3) A step of interconnecting the wiring layers between layers is included. Moreover, the manufacturing method of a circuit board may include the process of (4) removing a base material.

The step (3) is not particularly limited as long as the wiring layers can be interconnected between layers, but at least one of the steps of forming a via hole in the insulating layer and forming the wiring layer, and grinding or grinding the insulating layer to expose the wiring layer. It is preferable to be fair.

<Process (1)>

Step (1) is a step of preparing a substrate with a wiring layer, which includes a substrate and a wiring layer formed on at least one surface of the substrate. For example, a base material with a wiring layer has a 1st metal layer and a 2nd metal layer which are a part of a base material on both surfaces of a base material, respectively, It has a wiring layer on the surface on the opposite side to the surface on the side of a base material of a 2nd metal layer. In detail, a dry film (photosensitive resist film) is laminated|stacked on a base material, it exposes and develops using a photomask, and a pattern dry film is formed. After forming a wiring layer by the electrolytic plating method using the developed pattern dry film as a plating mask, the pattern dry film is peeled. In addition, it is not necessary to have a 1st metal layer and a 2nd metal layer.

Examples of the substrate include substrates such as glass epoxy substrates, metal substrates (stainless steel or cold rolled steel sheet (SPCC), etc.), polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, etc. , a metal layer such as copper foil may be formed on the surface of the substrate. Moreover, metal layers, such as a 1st metal layer and a 2nd metal layer (For example, Mitsui Kinzoku ultra-thin copper foil with carrier copper foil, brand name "Micro Thin") which can be peeled, may be formed in the surface.

The dry film is not particularly limited as long as it is a photosensitive dry film made of a photoresist composition, and for example, dry films such as novolac resin and acrylic resin can be used. A commercial item may be used for a dry film.

The conditions for laminating the substrate and the dry film are the same as the conditions for laminating the resin sheet in the step (2) to be described later so as to be embedded in the wiring layer, and the preferable ranges are also the same.

After laminating the dry film on the substrate, exposure and development are performed under predetermined conditions using a photomask to form a desired pattern on the dry film.

The line (circuit width)/space (width between circuits) ratio of the wiring layer is not particularly limited, but is preferably 20/20 µm or less (ie, the pitch is 40 µm or less) and 0.5/0.5 µm or more. The pitch need not be the same throughout the wiring layer. The minimum pitch of the wiring layers can be 40 µm or less.

After forming the pattern of the dry film, a wiring layer is formed and the dry film is peeled off. Here, formation of the wiring layer can be performed by the plating method using the dry film in which the desired pattern was formed as a plating mask.

The conductor material used for the wiring layer is not specifically limited. In a suitable embodiment, the wiring layer comprises one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. The wiring layer may be a single metal layer or an alloy layer, and the alloy layer is, for example, an alloy of two or more metals selected from the group described above (for example, a nickel-chromium alloy, a copper-nickel alloy, and a copper-titanium alloy). formed can be mentioned.

The thickness of the wiring layer depends on the desired design of the wiring board, but is preferably 3 mu m to 35 mu m. In the case where the step (3) of grinding or grinding the insulating layer and exposing the wiring layer to connect the wiring layers between layers is employed, it is preferable that the thicknesses of the wirings to be connected between the layers and the wirings not to be connected are different. The thickness of the wiring layer can be adjusted by repeating the above-described pattern formation. Although the thickness of the wiring layer (conductive filler) with the thickness among each wiring layer depends on the design of a desired wiring board, Preferably it is 100 micrometers or less and 2 micrometers or more. In addition, the wiring for interlayer connection may be made into a convex shape.

After forming the wiring layer, the dry film is peeled off. Peeling of a dry film can be performed using alkaline peeling solutions, such as a sodium hydroxide solution, for example. If necessary, unnecessary wiring patterns may be removed by etching or the like to form a desired wiring pattern. The pitch of the wiring layer to be formed is as described above.

<Process (2)>

Process (2) is a process of laminating|stacking the resin sheet of this invention on a base material with a wiring layer so that a wiring layer may be embedded in the resin composition layer, thermosetting it, and forming an insulating layer. In detail, the wiring layer of the base material with a wiring layer obtained in the above-mentioned process (1) is laminated|stacked so that it may be embedded in the resin composition layer of a resin sheet, and the resin composition layer of a resin sheet is thermosetted, and the insulating layer is formed.

Lamination of the wiring layer and the resin sheet can be performed by, for example, heat-bonding the resin sheet to the wiring layer from the support side after removing the protective film of the resin sheet. As a member (hereinafter also referred to as a "thermal crimp member") which heat-compresses a resin sheet to a wiring layer, a heated metal plate (SUS mirror plate etc.), a metal roll (SUS roll), etc. are mentioned, for example. Moreover, it is preferable not to press the thermocompression-bonding member directly to a resin sheet, but to base and press, such as an elastic material, such as a heat-resistant rubber, so that a resin sheet may fully follow the surface unevenness|corrugation of a wiring layer.

You may perform lamination|stacking of a wiring layer and a resin sheet by the vacuum lamination method after removing the protective film of a resin sheet. In the vacuum lamination method, the thermocompression bonding temperature is preferably in the range of 60° C. to 160° C., the thermocompression compression pressure is preferably in the range of 0.098 MPa to 1.77 MPa, and the thermocompression bonding time is preferably 20 seconds to 400 is the range of seconds. Lamination is preferably performed under reduced pressure conditions of a pressure of 13 hPa or less.

After lamination, the laminated resin sheet may be smoothed under normal pressure (under atmospheric pressure), for example, by pressing the thermocompression-bonding member from the support side. The press conditions of the smoothing process can be made into the conditions similar to the thermocompression-bonding conditions of the said lamination|stacking. In addition, you may carry out lamination|stacking and smoothing process continuously using the above-mentioned commercially available vacuum laminator.

After a resin composition layer is laminated|stacked on the base material with a wiring layer so that a wiring layer may be embedded, the resin composition layer is thermosetted and the insulating layer is formed. For example, although the thermosetting conditions of the resin composition layer vary depending on the type of resin composition, etc., the curing temperature may be in the range of 120°C to 240°C, and the curing time may be in the range of 5 minutes to 120 minutes. Before thermosetting a resin composition layer, you may preheat a resin composition layer at temperature lower than hardening temperature.

The support of the resin sheet may be peeled off after laminating and thermosetting the resin sheet on the substrate with a wiring layer, or may peel the support before laminating the resin sheet on the substrate with a wiring layer. In addition, you may peel a support body before the roughening process mentioned later.

<Process (3)>

Step (3) is a step of interconnecting the wiring layers between layers. In detail, it is a process of forming a via hole in an insulating layer, forming a conductor layer, and connecting a wiring layer between layers. Alternatively, the insulating layer is polished or ground, and the wiring layer is exposed to connect the wiring layers between layers.

In the case of employing a process of forming a via hole in the insulating layer and forming a conductor layer to connect the wiring layers between layers, the formation of the via hole is not particularly limited, but laser irradiation, etching, mechanical drilling, etc. are mentioned, but laser irradiation It is preferably carried out by This laser irradiation can be performed using any suitable laser processing machine using a carbon dioxide gas laser, a YAG laser, an excimer laser, or the like as a light source. Specifically, laser irradiation is performed on the surface side of the support body of the resin sheet, and a via hole is formed through the support body and the insulating layer to expose the wiring layer.

Conditions for laser irradiation are not particularly limited, and laser irradiation can be performed by any suitable process according to a conventional method according to the selected means.

Although the shape of the via hole, ie, the shape of the outline of an opening seen in the extending direction, is not specifically limited, Generally, it is set as circular (approximately circular).

After the via hole is formed, a so-called desmear process, which is a smear removal process in the via hole, may be performed. When the formation of the conductor layer described later is performed by a plating process, for example, a wet desmear treatment may be performed on the via hole, and when the conductor layer is formed by a sputtering process, for example, , a dry desmear process such as a plasma treatment process may be performed. In addition, a desmear process may serve also as a roughening process process.

Before forming the conductor layer, a roughening treatment may be performed on the via hole and the insulating layer. The harmonization process can employ|adopt well-known procedures and conditions normally performed. Plasma processing etc. are mentioned as an example of a dry roughening process, As an example of a wet roughening process, the swelling process by a swelling liquid, the roughening process by an oxidizing agent, and the method of performing the neutralization process by a neutralizing liquid in order are mentioned.

After the via hole is formed, a conductor layer is formed. The conductor material constituting the conductor layer is not particularly limited, and the conductor layer can be formed by any suitable method known in the art, such as plating, sputtering, and vapor deposition, and is preferably formed by plating. In a suitable embodiment, for example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. Moreover, when the support body in a resin sheet is metal foil, the conductor layer which has a desired wiring pattern can be formed by conventionally well-known techniques, such as a subtractive method. The conductor layer may have a single-layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated.

In the above description, the plating seed layer is formed on the surface of the insulating layer by electroless plating. Then, a mask pattern corresponding to the desired wiring pattern and exposing a portion of the plating seed layer is formed on the formed plating seed layer. An electrolytic plating layer is formed by electrolytic plating on the exposed plating seed layer. In that case, a filled via may be formed by filling a via hole by electroplating together with formation of an electrolytic plating layer. After the electrolytic plating layer is formed, the mask pattern is removed. Thereafter, the unnecessary plating seed layer may be removed by etching or the like to form a conductor layer having a desired wiring pattern. In addition, when forming a conductor layer, the dry film used for formation of a mask pattern is the same as that of the said dry film.

The conductor layer may include, for example, an electrode pad (land) on which an external terminal can be mounted, as well as a linear wiring. In addition, the conductor layer may be comprised only by the electrode pad.

Further, the conductor layer may be formed by forming an electrolytic plating layer and a filled via without using a mask pattern after forming the plating seed layer, and then performing patterning by etching.

In the case of employing a step of grinding or grinding the insulating layer and exposing the wiring layer to connect the wiring layers between layers, the wiring layer can be exposed as a polishing method or grinding method of the insulating layer. , a conventionally known polishing method or grinding method can be applied, and examples thereof include a chemical mechanical polishing method using a chemical mechanical polishing apparatus, a mechanical polishing method such as buffing, and a planar grinding method by rotating a whetstone. Similar to the step of forming a via hole in the insulating layer and forming the conductor layer to connect the wiring layers between layers, the smear removal step and the step of performing a roughening treatment may be performed, or the conductor layer may be formed. In addition, it is not necessary to expose all the wiring layers, and you may expose a part of wiring layers.

<Process (4)>

The manufacturing method of a circuit board is the process of removing a base material and forming the circuit board of this invention. The method of removing the substrate is not particularly limited. In one suitable embodiment, the substrate is peeled from the circuit board at the interface between the first and second metal layers, and the second metal layer is etched away with, for example, an aqueous copper chloride solution or the like. You may peel a base material in the state which protected the conductor layer with the protective film as needed.

[Semiconductor Chip Package]

A first aspect of the semiconductor chip package of the present invention is a semiconductor chip package in which a semiconductor chip is mounted on the circuit board of the present invention. A semiconductor chip package may be manufactured by bonding the semiconductor chip to the circuit board of the present invention.

As long as the terminal electrode of the semiconductor chip is conductor-connected to the circuit wiring of the circuit board, bonding conditions are not particularly limited, and well-known conditions used in flip-chip mounting of the semiconductor chip may be used. In addition, an insulating adhesive may be used for bonding between the semiconductor chip and the circuit board.

One suitable embodiment presses the semiconductor chip to the circuit board. As crimping|compression-bonding conditions, for example, crimping|compression-bonding temperature can be made into the range of 120 degreeC - 240 degreeC, and crimping|compression-bonding time can be made into the range of 1 second - 60 second.

Another preferred embodiment is to reflow and bond the semiconductor chip to the circuit board. As reflow conditions, it can be set as the range of 120 degreeC - 300 degreeC, for example.

It is also possible to obtain a semiconductor chip package by bonding a semiconductor chip to a circuit board and then filling the semiconductor chip with a mold underfill material, for example. The method of filling with a mold underfill material can be implemented by a well-known method. The resin composition or resin sheet of the present invention can also be used as a mold underfill material.

A second aspect of the semiconductor chip package of the present invention is a semiconductor chip package (Fan-out type WLP). A method of manufacturing a semiconductor chip package,

(A) the step of laminating a temporarily fixed film on the substrate,

(B) the process of temporarily fixing the semiconductor chip on the temporarily fixing film,

(C) the process of laminating|stacking the resin composition layer of the resin sheet of this invention on a semiconductor chip, or apply|coating the resin composition of this invention on a semiconductor chip, thermosetting, and forming a sealing layer;

(D) the step of peeling the substrate and the temporarily fixed film from the semiconductor chip,

(E) a step of forming a redistribution forming layer (insulating layer) on the surface of the semiconductor chip, the substrate and the temporarily fixed film,

(F) forming a conductor layer (rewiring layer) on the redistribution forming layer (insulating layer); and

(G) The process of forming a soldering resist layer on a conductor layer is included. Moreover, the manufacturing method of a semiconductor chip package may include the process of (H) dicing a some semiconductor chip package into individual semiconductor chip package, and dividing it into pieces.

<Process (A)>

Process (A) is a process of laminating|stacking a temporarily fixed film on a base material. Lamination conditions of a base material and a temporarily fixed film are the same as the lamination|stacking conditions of the wiring layer and resin sheet in the process (2) in the manufacturing method of a circuit board, and a preferable range is also the same.

The material used for the base material is not particularly limited. As a base material, a silicon wafer; glass wafer; glass substrate; metal substrates such as copper, titanium, stainless steel, and cold rolled steel sheet (SPCC); substrates (eg, FR-4 substrates) in which glass fibers are impregnated with an epoxy resin or the like and thermally cured; The board|substrate etc. which consist of bismaleimide triazine resin (BT resin) are mentioned.

Temporarily fixing film, while being able to peel from a semiconductor chip in the process (D) mentioned later, if a semiconductor chip can be temporarily fixed, a material will not be specifically limited. A commercial item can be used for a temporarily fixed film. As a commercial item, the Nitto Denko Co., Ltd. River Alpha etc. are mentioned.

<Process (B)>

A process (B) is a process of temporarily fixing a semiconductor chip on a temporarily fixing film. The temporary fixation of the semiconductor chip can be performed using a known device such as a flip chip bonder or a die bonder. The layout and number of arrangement of the semiconductor chip can be appropriately set according to the shape, size, number of production of the target semiconductor package, etc. of the temporarily fixed film, for example, can be temporarily fixed by arranging in a matrix of multiple rows and multiple columns can

<Process (C)>

A process (C) is a process of laminating|stacking the resin composition layer of the resin sheet of this invention on a semiconductor chip, or apply|coating the resin composition of this invention on a semiconductor chip, thermosetting, and forming a sealing layer. At a process (C), it is preferable to laminate|stack the resin composition layer of the resin sheet of this invention on a semiconductor chip, thermoset it, and form a sealing layer.

Lamination of the semiconductor chip and the resin sheet can be performed by, for example, heat-compressing the resin sheet to the semiconductor chip from the support side after removing the protective film of the resin sheet. As a member (henceforth a "thermal compression bonding member") which heat-compresses a resin sheet to a semiconductor chip, a heated metal plate (SUS mirror plate etc.), a metal roll (SUS roll), etc. are mentioned, for example. Moreover, it is preferable not to press the thermocompression-bonding member directly to a resin sheet, but to press through elastic materials, such as a heat-resistant rubber, so that a resin sheet may fully follow the surface unevenness|corrugation of a semiconductor chip.

In addition, you may perform lamination|stacking of a semiconductor chip and a resin sheet by the vacuum lamination method after removing the protective film of a resin sheet. The lamination conditions in the vacuum lamination method are the same as the lamination conditions of the wiring layer and the resin sheet in the step (2) in the circuit board manufacturing method, and the preferable ranges are also the same.

The support body of a resin sheet may peel after laminating|stacking and thermosetting a resin sheet on a semiconductor chip, and may peel a support body before laminating|stacking a resin sheet on a semiconductor chip.

As application|coating conditions of a resin composition, it is the same as the application|coating conditions at the time of forming the resin composition layer in the resin sheet of this invention, and a preferable range is also the same.

<Process (D)>

A process (D) is a process of peeling a base material and a temporarily fixed film from a semiconductor chip. The peeling method can be suitably changed depending on the material of the temporarily fixed film, etc., for example, by heating the temporarily fixed film, foaming (or expanding) to peel the method, and irradiating ultraviolet rays from the substrate side, the adhesive force of the temporarily fixed film The method of peeling by lowering|reducing , etc. are mentioned.

In the method of peeling the temporarily fixed film by heating, foaming (or expanding), heating conditions are usually at 100 ° C. to 250 ° C. for 1 second to 90 seconds or 5 minutes to 15 minutes. In addition, in the method of peeling by irradiating ultraviolet rays from the substrate side to reduce the adhesive force of the temporarily fixed film, the irradiation amount of ultraviolet rays is usually 10mJ/cm 2 to 1000mJ/cm 2 .

<Process (E)>

A process (E) is a process of forming a redistribution forming layer (insulating layer) in the surface which peeled the base material and temporarily fixed film of a semiconductor chip.

The material for forming the redistribution forming layer (insulating layer) is not particularly limited as long as it has insulating properties when the redistribution forming layer (insulating layer) is formed. Do. As the thermosetting resin, a resin composition having the same composition as the resin composition for forming the resin sheet of the present invention may be used.

After formation of the redistribution forming layer (insulating layer), a via hole may be formed in the redistribution forming layer (insulating layer) for interlayer connection between a semiconductor chip and a conductor layer to be described later.

In forming the via hole, when the material for forming the redistribution layer (insulation layer) is a photosensitive resin, first, an active energy ray is irradiated to the surface of the redistribution layer (insulation layer) through a mask pattern, and the most wiring layer of the irradiated portion is photocured.

As an active energy ray, an ultraviolet-ray, a visible light ray, an electron beam, X-ray etc. are mentioned, for example, Especially an ultraviolet-ray is preferable. The irradiation amount of ultraviolet rays and irradiation time can be suitably changed according to the photosensitive resin. As the exposure method, either a contact exposure method in which the mask pattern is exposed in close contact with the redistribution forming layer (insulating layer) or a non-contact exposure method in which the mask pattern is exposed using parallel light without being in close contact with the redistribution forming layer (insulating layer). You may use it.

Then, the rewiring forming layer (insulating layer) is developed and the unexposed portion is removed to form a via hole. Development is suitable for both wet development and dry development. A well-known developing solution can be used for the developing solution used by wet image development.

As a method of development, a dip method, a paddle method, a spray method, a brushing method, a scraping method, etc. are mentioned, for example, From a viewpoint of resolution, a paddle method is suitable.

When the material for forming the redistribution forming layer (insulating layer) is a thermosetting resin, the formation of the via hole is not particularly limited, and laser irradiation, etching, mechanical drilling, etc. may be mentioned, but it is preferably performed by laser irradiation. Laser irradiation can be performed using any suitable laser processing machine using a carbon dioxide laser, a UV-YAG laser, an excimer laser, or the like as a light source.

The shape of the via hole, that is, the shape of the outline of the opening when viewed in the extension direction is not particularly limited, but is generally circular (approximately circular). The top diameter of the via hole (diameter of the opening on the surface of the rewiring forming layer (insulating layer)) is preferably 50 µm or less. Although the minimum is not specifically limited, Preferably it is 10 micrometers or more.

<Process (F)>

The step (F) is a step of forming a conductor layer (rewiring layer) on the rewiring forming layer (insulating layer). The method of forming the conductor layer on the rewiring forming layer (insulating layer) is the same as the method of forming the conductor layer after forming a via hole in the insulating layer in step (3) in the circuit board manufacturing method, and the preferred range is the same. Do. Alternatively, the steps (E) and (F) may be repeated, and the conductor layers (rewiring layer) and the redistribution forming layer (insulating layer) may be alternately stacked (build-up).

<Process (G)>

A process (G) is a process of forming a soldering resist layer on a conductor layer.

The material which forms a soldering resist layer will not be specifically limited if it has insulation at the time of soldering resist layer formation, A viewpoint of the ease of manufacture of a semiconductor chip package to photosensitive resin and thermosetting resin are preferable. As a thermosetting resin, you may use the resin composition of the same component as the resin composition for forming the resin sheet of this invention.

In addition, in the process (G), you may perform the bumping process which forms a bump as needed. The bumping process may be performed by a known method such as solder ball or solder plating. In addition, the formation of a via hole in the bumping process may be performed in the same manner as in the process (E).

<Process (H)>

The manufacturing method of a semiconductor chip package may include the process (H) in addition to the process (A)-(G). The step (H) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and separating them into pieces.

A third aspect of the semiconductor chip package of the present invention is a semiconductor chip package in which a redistribution forming layer (insulating layer) and a soldering resist layer in a semiconductor chip package (Fan-out type WLP) are manufactured from the resin composition or resin sheet of the present invention. am.

[Semiconductor device]

Examples of the semiconductor device on which the semiconductor chip package of the present invention is to be mounted include electrical appliances (for example, computers, mobile phones, smartphones, tablet-type devices, wearable devices, digital cameras, medical devices, televisions, etc.) and Various semiconductor devices provided in vehicles (eg, motorcycles, automobiles, electric trains, ships, aircraft, etc.) etc. are mentioned.

Example

Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited to these Examples. In the following description, "parts" and "%" mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

[Synthesis Example 1]

<Production of Elastomer A>

Into a flask equipped with a stirring device, a thermometer and a condenser, 368.41 g of ethyl diglycol acetate and 368.41 g of Solvesso 150 (aromatic solvent, manufactured by ExxonMobil) as a solvent were injected, and 100.1 g (0.4 g) of diphenylmethane diisocyanate was added. mol) and polycarbonate diol (number average molecular weight: about 2000, hydroxyl equivalent: 1000, non-volatile content: 100%, “C-2015N” manufactured by Kuraray Co., Ltd.) 400 g (0.2 mol) were injected and heated at 70° C. for 4 hours The reaction was carried out. Next, 195.9 g (0.2 mol) of nonylphenol novolak resin (hydroxyl equivalent 229.4 g/eq, average 4.27 functionality, average calculated molecular weight 979.5 g/mol) and 41.0 g (0.1 mol) of ethylene glycol bisanhydrotrimellitate were injected Then, it heated up to 150 degreeC over 2 hours, and was made to react for 12 hours. Confirmation of the disappearance of the NCO peak of 2250 cm -1 from FT-IR was performed. It was regarded as the end point of the reaction by confirming the disappearance of the NCO peak, and the reaction product was cooled to room temperature and then filtered through a 100-mesh filter cloth to obtain a resin having a polycarbonate structure (non-volatile content: 50% by mass). The number average molecular weight was 6100.

(Production of cured product for evaluation)

A glass cloth-based epoxy resin double-sided copper-clad laminate (“R5715ES” manufactured by Panasonic Co., Ltd., thickness 0.7 mm, 255 mm square), and the four sides were fixed with polyimide adhesive tape (width 10 mm) (henceforth "fixed PET film").

PET film (“Lumiror R80” manufactured by Toray Co., Ltd., 38 μm thick, softening point 130), in which the resin varnish produced in Examples and Comparative Examples was treated with an alkyd resin mold release agent (“AL-5” manufactured by Lintec Co., Ltd.) ℃, hereinafter “Releasable PET”), applied with a die coater so that the thickness of the resin composition layer after drying becomes 40 μm, and dried at 80° C. to 120° C. (average 100° C.) for 10 minutes to obtain an adhesive film. Each adhesive film (thickness 40 μm, 200 mm each) was applied with a batch vacuum pressurized laminator (Nikko Materials Co., Ltd. 2-stage build-up laminator, CVP700), the resin composition layer was fixed with the release agent-treated side of the PET film A resin sheet with a support was obtained by laminating at the center so as to be in contact with each other. After lamination process pressure-reduced for 30 second and air pressure was 13 hPa or less, it was performed by crimping|bonding at 100 degreeC and pressure 0.74 MPa for 30 second.

Then, after being put into an oven at 100° C. under a temperature condition of 100° C. for 30 minutes, then, under a temperature condition of 175° C., it was transferred to an oven at 175° C. and thermosetted for 30 minutes. Then, the board|substrate was taken out in room temperature atmosphere, and after peeling mold release PET from the resin sheet with a support body, it was made to thermoset under hardening conditions for 60 minutes after injecting|throwing-in further 180 degreeC oven.

After thermosetting, the polyimide adhesive tape was peeled off, the cured product was separated from the glass cloth-based epoxy resin double-sided copper clad laminate, and the PET film (“501010” manufactured by Lintec Co., Ltd.) was also peeled to obtain a sheet-like cured product. The obtained hardened|cured material is called "hardened|cured material for evaluation".

<Measurement of elastic modulus and tensile strength at break>

The cured product for evaluation was cut out in a dumbbell-shaped No. 1 shape to obtain a test piece. The test piece was subjected to tensile strength measurement using a tensile tester "RTC-1250A" manufactured by Orientec Co., Ltd., and the elastic modulus and tensile strength at break at 23°C were determined. The measurement was performed based on JISK7127. This operation was performed 3 times, and the average value is shown in a table|surface.

<Strength evaluation>

After attaching the forming tape side of the temporary fixing film (River Alpha No. 31950E, thermal release tape manufactured by Nitto Denko Co., Ltd.) to the wafer with a roll laminator on an 8-inch silicon wafer, on the base adhesive side of River Alpha, a silicon chip (DIE size) 9x6mm, height 150um) were arranged at equal intervals.

PET film (“Lumiror R80” manufactured by Toray Co., Ltd., 38 μm thick, softening point 130), in which the resin varnish produced in Examples and Comparative Examples was release-treated with an alkyd resin mold release agent (“AL-5” manufactured by Lintec Co., Ltd.) ℃, hereinafter "Releasable PET") was applied with a die coater so that the thickness of the resin composition layer after drying became 200 μm, and dried at 80° C. to 120° C. (average 100° C.) for 10 minutes to obtain an adhesive film. The obtained adhesive film was laminated on the silicon chip side of the above-mentioned silicon chip-attached wafer using a batch vacuum pressure laminator (Nikko Materials Co., Ltd. 2-stage build-up laminator, CVP700), and the silicon chip was sealed. After heating the silicon wafer in an oven at 150° C. for 1 hour, the silicon wafer is heated on a hot plate at 200° C., the silicon wafer and Riva Alpha are peeled from the forming tape, and the resin sealed with the Riva Alpha base adhesive surface. The interface was peeled off by hand to obtain a resin wafer in which the silicon chip was embedded in the resin. In the above process, those in which lack of resin and cracks occurred were denoted by "x", and those in which lack of resin and cracks did not occur were denoted by "○".

<Adhesiveness evaluation>

A PET film (Toray Co., Ltd.) prepared by depositing 1000 Å of silicon nitride on an 8-inch silicon wafer, and releasing the resin varnish produced in Examples and Comparative Examples with an alkyd resin-based release agent (“AL-5” manufactured by Lintech Co., Ltd.) Co., Ltd. manufacture "Lumiror R80", thickness 38㎛, softening point 130℃, hereinafter "Releasable PET"), apply with a die coater so that the thickness of the resin composition layer after drying becomes 20㎛, 80 ℃ to 120 ℃ (Average 100 ℃) and dried for 10 minutes to obtain an adhesive film. The obtained adhesive film was laminated to the said wafer using the batch type vacuum pressure laminator (Nikko Materials Co., Ltd. product 2 stage build-up laminator, CVP700). After thermosetting in an oven at 180 ° C. for 1 hour, according to "JIS K5400-8.5 (1990)", the resin composition layer was cross-cut (100 pieces) on a 1 mm x 1 mm checkerboard, followed by a pressure cooker treatment (121 ° C.) /humidity 100%/100 hours), a tape peel test was performed, and the number of cells in which the resin was peeled was counted. 0-5 pieces of peeled cells were "○", 6-19 pieces were made into "Δ", and 20 or more pieces were made into "x".

<Warp evaluation>

PET film (“Lumiror R80” manufactured by Toray Co., Ltd., 38 μm thick, softening point 130), in which the resin varnish produced in Examples and Comparative Examples was release-treated with an alkyd resin mold release agent (“AL-5” manufactured by Lintec Co., Ltd.) ℃, hereinafter referred to as "Releasable PET"), applied with a die coater so that the thickness of the resin composition layer after drying becomes 300 μm, and dried at 80° C. to 120° C. (average 100° C.) for 10 minutes to obtain an adhesive film. The obtained adhesive film was laminated on a 12-inch silicon wafer (thickness 775 um) using a batch vacuum pressurized laminator (Nikko Materials Co., Ltd. 2-stage build-up laminator, CVP700) and heated at 180° C. for 1 h to cure the resin. A wafer with resin was created. A wafer with resin was placed on a flat surface with the resin side facing up, and the amount of warpage was measured. The curvature amount of the location with the largest curvature made less than 2 mm into (circle), and 2 mm or more made x.

[Example 1]

3 parts of bisphenol A epoxy resin ("828EL" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent about 186), 10 parts of elastomer A, phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Co., Ltd., 30% by mass of solid content) Cyclohexanone: 1:1 solution of methyl ethyl ketone (MEK)) 17 parts, dicyclopentadiene type epoxy resin ("HP-7200" manufactured by DIC, epoxy equivalent 258) 3 parts, carbodiimide compound (Nissinbo Corporation) Chemical Co., Ltd. "V-07", carbodiimide equivalent 200, toluene solution of 50 mass % of nonvolatile component) 4 parts, aminosilane type coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) surface-treated 115 parts of spherical silica A (average particle size of 1.7 μm, specific surface area (m2/g) 2.7 μm), polyphenylene ether oligomer (“OPE-1000” manufactured by Mitsubishi Gas Chemical Co., Ltd., toluene solution with a solid content of about 52%; Phenolic hydroxyl equivalent: 435 g/eq) 9.6 parts, flame retardant (“HCA-HQ” manufactured by Sanko Corporation, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene -10-oxide, average particle diameter of 2 µm) 1.5 parts, curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., "2P4MZ-5M", 1-benzyl-2-phenylimidazole, MEK solution having a solid content of 5% by mass) 3 parts are mixed Then, 100 parts of cyclohexanone was uniformly dispersed with a high-speed rotary mixer, filtered through a cartridge filter ("SHP050" manufactured by ROKITECHNO), and a resin varnish was produced.

[Example 2]

3 parts of bisphenol A epoxy resin ("828EL" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent about 186), 10 parts of elastomer A, phenoxy resin ("YX6954BH30" manufactured by Mitsubishi Chemical Co., Ltd. "YX6954BH30", solid content of 30% by mass) Cyclohexanone: 1:1 solution of methyl ethyl ketone (MEK)) 17 parts, dicyclopentadiene type epoxy resin ("HP-7200" manufactured by DIC, epoxy equivalent 258) 3 parts, carbodiimide compound (Nissinbo Corporation) Chemical Co., Ltd. "V-07", carbodiimide equivalent 200, toluene solution of 50 mass % of nonvolatile component) 4 parts, aminosilane type coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) surface-treated 115 parts of spherical silica A (average particle size of 1.7 µm, specific surface area (m2/g) of 2.7 µm) 115 parts, a phenol novolac curing agent containing triazine skeleton (“LA-7054” manufactured by DIC Co., Ltd., hydroxyl equivalent of about 125, solid content of 60 % MEK solution) 3.3 parts, methyl ethyl ketone solution (solid content: 50%) of naphthol-based curing agent (“SN-485” manufactured by Shin-Nittetsu Sumikin Chemical Co., Ltd., hydroxyl equivalent: 215 g/eq) (solid content: 50%) 6 parts, flame retardant (“HCA-HQ” manufactured by Sanko Corporation, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle size 2 μm) 1.5 parts, 3 parts of hardening accelerator ("2P4MZ-5M" manufactured by Shikoku Kasei Co., Ltd., 1-benzyl-2-phenylimidazole, MEK solution having a solid content of 5% by mass) is mixed, and 100 parts of cyclohexanone is uniformly dispersed with a high-speed rotary mixer and filtered with a cartridge filter ("SHP050" manufactured by ROKITECHNO) to prepare a resin varnish.

[Example 3]

3 parts of bisphenol A epoxy resin ("828EL" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent about 186), 10 parts of elastomer A, phenoxy resin ("YX6954BH30" manufactured by Mitsubishi Chemical Co., Ltd. "YX6954BH30", solid content of 30% by mass) Cyclohexanone: 1:1 solution of methyl ethyl ketone (MEK) 27 parts, dicyclopentadiene type epoxy resin ("HP-7200" manufactured by DIC, epoxy equivalent 258) 3 parts, carbodiimide compound (Nissinbo Corporation) Chemical Co., Ltd. "V-07", carbodiimide equivalent 200, toluene solution of 50 mass % of nonvolatile component) 4 parts, aminosilane type coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) surface-treated 115 parts of spherical silica A (average particle size of 1.7 µm, specific surface area (m2/g) of 2.7 µm) 115 parts, a phenol novolac curing agent containing triazine skeleton (“LA-7054” manufactured by DIC Co., Ltd., hydroxyl equivalent of about 125, solid content of 60 % MEK solution) 5 parts, flame retardant (“HCA-HQ” manufactured by Sanko Corporation, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide , average particle diameter 2 µm) 1.5 parts, a curing accelerator (manufactured by Shikoku Kasei Co., Ltd., "2P4MZ-5M", 1-benzyl-2-phenylimidazole, MEK solution with a solid content of 5 mass %) 3 parts are mixed, and cyclohexa 100 parts of paddy fields were uniformly dispersed with a high-speed rotary mixer, and filtered through a cartridge filter ("SHP050" manufactured by ROKITECHNO) to prepare a resin varnish.

[Example 4]

3 parts of bisphenol A epoxy resin ("828EL" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent about 186), 10 parts of elastomer A, dicyclopentadiene type epoxy resin ("HP-7200" manufactured by DIC Corporation, epoxy equivalent 258) ) 3 parts, bisphenol F-type phenoxy resin (“FX-316” manufactured by Shin-Nittetsu Sumikin Chemical Co., Ltd.) 5 parts, polyphenylene ether oligomer (“OPE-1000” manufactured by Mitsubishi Gas Chemical Co., Ltd. solid content About 52% toluene solution, phenolic hydroxyl group equivalent: 435 g/eq) 9.6 parts, carbodiimide compound (Nissinbo Chemical Co., Ltd. "V-07", carbodiimide equivalent 200, 50 mass% of nonvolatile components Toluene solution) 4 parts, 115 parts of spherical silica A (average particle size of 1.7 µm, specific surface area (m2/g) 2.7 µm) surface-treated with an aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) 115 parts, a flame retardant ( "HCA-HQ" manufactured by Sanko Corporation, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle size 2 µm) 1.5 parts, cured 3 parts of accelerator ("2P4MZ-5M" manufactured by Shikoku Kasei Co., Ltd., 1-benzyl-2-phenylimidazole, MEK solution having a solid content of 5% by mass) is mixed, and 100 parts of cyclohexanone is uniformly dispersed with a high-speed rotary mixer and filtered with a cartridge filter ("SHP050" manufactured by ROKITECHNO) to prepare a resin varnish.

[Example 5]

3 parts of bisphenol A epoxy resin (“828EL” manufactured by Mitsubishi Chemical Co., Ltd., approx. 186 epoxy equivalent), 5 parts of elastomer A, phenoxy resin containing flexible structure (“YX7180BH40” manufactured by Mitsubishi Chemical Co., Ltd., solid content 40) 25 parts by mass of cyclohexanone: a 1:1 solution of MEK) 25 parts, dicyclopentadiene type epoxy resin ("HP-7200" manufactured by DIC, epoxy equivalent 258) 3 parts, carbodiimide compound (Nissinbo Chemical (Nissinbo Chemical) Note) Manufactured "V-07", carbodiimide equivalent weight 200, toluene solution containing 50 mass% of nonvolatile components) 4 parts, spherical silica surface-treated with an aminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) 120 parts A (average particle diameter 1.7 μm, specific surface area (m2/g) 2.7 μm) 120 parts, triazine skeleton-containing phenol novolac curing agent (“LA-7054” manufactured by DIC Co., Ltd., hydroxyl equivalent of about 125, solid content of 60% MEK solution) 8.3 parts, flame retardant (“HCA-HQ” manufactured by Sanko Corporation, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average Particle size: 2 µm), 3 parts of a curing accelerator (“2P4MZ-5M” manufactured by Shikoku Kasei Co., Ltd., 1-benzyl-2-phenylimidazole, MEK solution having a solid content of 5% by mass) are mixed, and cyclohexanone 100 The part was uniformly dispersed with a high-speed rotating mixer and filtered through a cartridge filter ("SHP050" manufactured by ROKITECHNO) to prepare a resin varnish.

[Comparative Example 1]

3 parts of bisphenol A epoxy resin ("828EL" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent about 186), 15 parts of elastomer A, dicyclopentadiene type epoxy resin ("HP-7200" manufactured by DIC, 258 epoxy equivalent) ) 3 parts, carbodiimide compound ("V-07" manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide equivalent 200, toluene solution containing 50 mass % of nonvolatile components) 4 parts, aminosilane-based coupling agent (Shin-Etsu Chemical) 115 parts of spherical silica A (average particle size of 1.7 µm, specific surface area (m2/g) 2.7 µm) surface-treated with "KBM573" manufactured by Kogyo Corporation, polyphenylene ether oligomer ("OPE-" manufactured by Mitsubishi Gas Chemical Co., Ltd.) 1000", a toluene solution with a solid content of about 52%, phenolic hydroxyl equivalent: 435 g/eq) 9.6 parts, a flame retardant ("HCA-HQ" manufactured by Sanko Corporation, 10-(2,5-dihydroxyphenyl)-10-hydro -9-oxa-10-phosphaphenanthrene-10-oxide, average particle diameter of 2 μm) 1.5 parts, a curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., “2P4MZ-5M”, 1-benzyl-2-phenylimidazole, 3 parts of MEK solution with a solid content of 5 mass %) were mixed, 100 parts of cyclohexanone were uniformly dispersed with a high-speed rotary mixer, and filtered with a cartridge filter ("SHP050" manufactured by ROKITECHNO) to prepare a resin varnish.

[Comparative Example 2]

3 parts of bisphenol A epoxy resin ("828EL" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent about 186), 3 parts of dicyclopentadiene type epoxy resin ("HP-7200" manufactured by DIC, epoxy equivalent 258), 3 parts of bisphenol 15 parts of F-type phenoxy resin (“FX-316” manufactured by Shin-Nittetsu Sumikin Chemical Co., Ltd.), a phenol novolac curing agent containing a triazine skeleton (“LA-7054” manufactured by DIC Co., Ltd., hydroxyl equivalent of about 125 , MEK solution having a solid content of 60%) 8.3 parts, a carbodiimide compound (“V-07” manufactured by Nisshinbo Chemical Co., Ltd., a carbodiimide equivalent of 200, a toluene solution containing 50% by mass of a nonvolatile component) 4 parts, aminosilane 115 parts of spherical silica A (average particle size 1.7 µm, specific surface area (m2/g) 2.7 µm) surface-treated with a coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), a flame retardant (“HCA-HQ” manufactured by Sanko Corporation) , 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle diameter 2 μm) 1.5 parts, curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd.) , "2P4MZ-5M", 1-benzyl-2-phenylimidazole, MEK solution having a solid content of 5% by mass) 3 parts were mixed, 100 parts of cyclohexanone were uniformly dispersed with a high-speed rotary mixer, and a cartridge filter (ROKITECHNO) It filtered by manufacture "SHP050"), and the resin varnish was produced.

[Comparative Example 3]

3 parts of bisphenol A epoxy resin ("828EL" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent about 186), 10 parts of elastomer A, phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Co., Ltd., 30% by mass of solid content) Cyclohexanone: 1:1 solution of methyl ethyl ketone (MEK)) 17 parts, dicyclopentadiene type epoxy resin ("HP-7200" manufactured by DIC, epoxy equivalent 258) 3 parts, aminosilane coupling agent (Shin-Etsu) 115 parts of spherical silica A (average particle diameter of 1.7 µm, specific surface area (m2/g) 2.7 µm) surface-treated with "KBM573" manufactured by Kagaku Kogyo Co., Ltd., polyphenylene ether oligomer (manufactured by Mitsubishi Gas Chemical Co., Ltd. " OPE-1000", toluene solution with a solid content of about 52%, phenolic hydroxyl equivalent: 435 g/eq) 9.6 parts, flame retardant ("HCA-HQ" manufactured by Sanko Corporation, 10-(2,5-dihydroxyphenyl)-10 -Hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle diameter 2㎛) 1.5 parts, curing accelerator ("2P4MZ-5M" manufactured by Shikoku Kasei Kogyo Co., Ltd., 1-benzyl-2-phenylimidazole , MEK solution having a solid content of 5% by mass) 3 parts were mixed, 100 parts of cyclohexanone were uniformly dispersed with a high-speed rotary mixer, and filtered with a cartridge filter ("SHP050" manufactured by ROKITECHNO) to prepare a resin varnish.

[Production Example 1]

<Production of resin sheet for fan-out type WLP>

On a polyethylene terephthalate film (thickness 38 μm), the resin varnish described in Example 1 is applied with a die coater so that the thickness of the resin composition layer after drying becomes 200 μm, and dried at 80 to 120° C. (average 100° C.) for 10 minutes. Thus, a resin sheet was obtained.

When the sealing layer of the fan-out type WLP was fabricated using the resin sheet, it was found that it had sufficient performance as the fan-out type WLP.

[Production Example 1]

<Production of resin sheet for interlayer insulation>

On a polyethylene terephthalate film (thickness 38 μm), the resin varnish described in Example 1 is applied with a die coater so that the thickness of the resin composition layer after drying becomes 200 μm, and dried at 80 to 120° C. (average 100° C.) for 10 minutes. Thus, a resin sheet was obtained.

When the interlayer insulating layer of a circuit board was produced using the said resin sheet, it turned out that the circuit board of this invention has sufficient performance.

Claims (14)

A resin composition comprising (a) an elastomer having a polycarbonate structure in a molecule, (b) an epoxy resin, (c) an inorganic filler, (d) a phenoxy resin, and (e) a carbodiimide compound,
(a) a component is a resin having a structure represented by the formula (1-a) and a structure represented by the formula (1-b),
The resin composition in which (a) component has a functional group which can react with (b) component.
Formula (1-a)

Formula (1-b)

In the above formula,
R1 represents a residue excluding the hydroxyl group of the polycarbonate diol, R2 represents a residue excluding the carboxyl group or acid anhydride group of a polybasic acid or anhydride thereof, and R3 represents a residue other than the isocyanate group of the diisocyanate compound. The resin composition according to claim 1, wherein the content of the component (c) is 75% by mass to 95% by mass, when the nonvolatile component of the resin composition is 100% by mass. The resin composition of Claim 1 or 2 whose content of (a) component is 30 mass % - 85 mass %, when the non-volatile component of the resin composition except (c) component makes 100 mass %. The resin composition according to claim 1 or 2, wherein the cured product obtained by thermosetting the resin composition at 180°C for 1 hour has an elastic modulus at 23°C of 8 GPa or more. delete delete The resin composition according to claim 1 or 2, wherein the component (a) has a phenolic hydroxyl group. The resin composition according to claim 1 or 2, further comprising (f) a curing agent, and the curing agent is at least one selected from phenol-based curing agents. The resin composition according to claim 1 or 2, which is a resin composition for semiconductor chip package insulating layers. A resin sheet having a support and a resin composition layer formed on the support and comprising the resin composition according to claim 1 . The resin sheet according to claim 10, which is a resin sheet for an insulating layer of a semiconductor chip package. The circuit board containing the insulating layer formed with the hardened|cured material of the resin composition of Claim 1 or 2. The semiconductor chip package in which the semiconductor chip was mounted on the circuit board of Claim 12. A semiconductor chip package comprising a semiconductor chip sealed with the resin composition according to claim 1 or the resin sheet according to claim 10.